JPH03186840A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility, the light-fastness of color images and processing stability by incorporating specific couplers dispersed by using at least one of chlorinated paraffin having >=175 deg.C b. p. under atm. pressure into silver halide emulsion layers. CONSTITUTION:At least one of the couplers expressed by formula I are dispersed by using at least one of the chlorinated paraffin having >=175 deg.C b. p. under atm. pressure and are incorporated into the silver halide emulsion layers. In the formula I, Za, Zb respectively denote =CH-, =N-, etc.; R1 denotes a hydrogen atom or substituent; R2 denotes a substituent; X denotes a hydrogen atom or the group which can be eliminated by coupling reaction with the oxidant of an arom. primary amine developing agent. The silver halide photographic sensitive material which is excellent in the color reproducibility and is improved in the light-fastness of the magenta color images is obtd. in this way.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it relates to a silver halide color photographic light-sensitive material, which has excellent color reproducibility, improved color image light fastness, and excellent processing stability. This invention relates to silver color photographic materials. (Prior Art) Subtractive color photography is based on the oxidation products of a color developing agent produced by reducing silver halide exposed to light by an aromatic primary amine color developing agent, yellow, magenta,
By coupling with each cyan dye-forming coupler, yellow, magenta, and cyan dyes, which are complementary colors of blue, green, and red, are formed, and a color image is formed. Substantially non-diffusive couplers contained in light-sensitive materials are usually prepared using substantially water-insoluble high-boiling organic solvents such as phosphate esters or phthalate esters, or in combination with complementary color solvents as necessary. The silver halide emulsion is then dissolved and added to the silver halide emulsion. The basic properties required of a non-diffusible coupler include not only the ability to color and form a dye, but also a fast rate of formation of the dye, high solubility in high-boiling organic solvents, and silver halide photography. It is desired to have excellent properties such as good dispersibility and stability in emulsions, and good light resistance, heat resistance, and moisture resistance of the color images produced. (Problem to be solved by the invention) U.S. Patent No. 3,725,067, British Patent No. 1.252
, 418, and 1H-pyrazolo described in British Patent No. 1,334,515.

[5.1cl [1,,2,4]
Triazole coupler, European Patent No. 119,860
1H-pyrazolo[1,5-bl El
, 2.4] ) Riazole coupler, RD2422
0 (June 1984) 1H-pyrazolo [
1,5-dl tetrazole coupler and RD242
30 (June 1984) [
Formed from 1,5-bl pyrazole couplers etc.
Magenta dye has little harmful side absorption around 430 nm.
This is good for color reproduction, and heat and humidity can damage uncolored areas.
It is preferable because it rarely causes yellow suiten.
It's something new. However, the azomeres formed from these couplers
Chin dyes have low fastness to light and are not suitable for color photographic materials.
In particular, it impairs the performance of printed color photographic materials.
It was something. Additionally, this coupler may be accidentally exposed to bleach during processing.
A small amount of bleach-fixing solution or bleach-fixing solution may be mixed in during the night of color development, resulting in halogen.
Processing with a color developing solution that has increased the solubility of silver
When treated, the concentration of the coloring dye decreases significantly and
There was a problem with desensitization. JP-A-61-84641 discloses high boiling point chlorinated paraffin.
Dispersibility and solubility are improved by using as a coupler solvent.
It is also described that the color image stability is improved. On the other hand, JP-A-61-65245, JP-A No. 62-89961
The number has at least one substituted alkyl group as a substituent.
The pyrazoloazole magenta coupler is sensitive to light.
It is stated that the fastness is improved and the color reproducibility is also excellent.
ing. However, this product has the disadvantage of poor processing stability.
It had Using a color developer that is not particularly fatigued
Very little bleach or bleach-fix solutions (e.g. EDT)
If A) is mixed with ferric iron, the coloring pigment will be lost.
In many cases, the major drawback was that the concentration of the coloring pigment decreased.
. Therefore, the first object of the present invention is to have excellent color reproducibility and
Halogen with significantly improved light fastness of magenta images
The purpose of the present invention is to provide a silver oxide photographic material. The second purpose of the present invention is to prevent bleach from being mixed in during running.
There is little loss of color image density even when processed with color developer,
A pyrazoloazole cap with improved color image light fastness.
To provide a silver halide photographic light-sensitive material containing silver.
There it is. (Means for Solving the Problems) The objects of the present invention have been achieved by the following techniques. (1) At least one silver halide emulsion layer on the support
In a silver halide color photographic light-sensitive material provided with
, in the silver halide emulsion layer is represented by the following formula (I)-6.
at least one of the couplers that is present has a boiling point of 175 at normal pressure
℃ or higher using at least one chlorinated paraffin.
Silver halide color characterized by containing dispersed
Photographic material. General formula (I) (wherein Za and zb each represent =CH2 =C- or =N-, and R1 is a hydrogen atom or a
represents a substituent, R2 represents a substituent, and X represents a hydrogen atom or
Coupling with oxidized aromatic primary amine developer
Represents a vine group that leaves due to reaction. Za=Zb is carbon-
For carbon double bonds, if it is part of an aromatic ring
including. Even if R,, R2 or X forms a dimer or more multimer,
good. However, if two R2s exist in the same molecule, they are the same
But they can be different. Also, I) R2 in the same molecule
or II) R if R2 is present in the same molecule, and
At least one of R2 is pyrazoloazole via a secondary or tertiary carbon atom.
Represents a group bonded to a ring. ) (2) The following general formula (II) is present in the silver halide emulsion layer.
characterized by containing at least one kind of compound represented by
The silver halide color photographic material according to (1) above, wherein
fee. General formula (11) (wherein, R10, R11, R12 and R13 are carbon atoms
an alkyl group having 1 to 18 molecules, R14 is a hydrogen atom or
It is an alkyl group having 1 to 12 carbon atoms, and n is 1 to 3.
is an integer. However, when n is 2 to 3, each RI4 is the same.
They may be the same or different; when n is 1, R8 is
It is the alkyl group mentioned above. ) The pyrazoloazole compound represented by the general formula (1) below
The puller will be explained in detail. In general formula (1), multimer means two or more molecules in one molecule.
means having a group represented by general formula (1)
This includes bis bodies and polymer couplers. here
The polymer coupler has a moiety represented by the general formula (I).
Monomers with (preferably those with vinyl groups, below)
A homopolymer consisting only of vinyl monomers (called vinyl monomers) may also be used.
Oxidation products of aromatic primary amine developer and cup
Copolymer with non-ringing, non-chromogenic ethylene-like monomer
You can also make a ma. The couplers represented by the general formula (I) are each represented by the general formula (
I-1), (1-2), (r-3), (I-4) and (
1-5). (I ■) (I 2) 4 (I-3) (I 4) (I-5) Couplers represented by general formulas (I-1) to (I-5)
Among them, preferred for the purpose of the present invention are format (I-1),
(I-2) and (I-3), more preferred
is represented by the general formula (1-2). Substituents of general formulas (I-1) to (I-3>, R3,
R4 and R6 are hydrogen atoms, halogen atoms, alkyl groups,
Aryl group, heterocyclic group, cyano group, alkoxy group,
lyloxy group, heterocyclic oxy group, acyloxy group,
Carbamoyloxy group, silyloxy group, sulfonyloxy group
xy group, acylamino group, anilino group, ureido group,
Mido group, sulfamoylamino group, carbamoylamino group
group, alkylthio group, arylthio group, heterocyclic thio group
, alkoxycarbonylamino group, aryloxycar
Bonylamino group, sulfonamide group, carbamoyl group,
Acyl group, sulfamoyl group, sulfonyl group, sulfyl group
Nyl group, alkoxycarbonyl group, aryloxycar
Represents a bonyl group, the least of R,, R4 or R6
One is a pyramid via a secondary or tertiary carbon atom.
Represents a group bonded to the zoroazole ring. Substituents R6 in general formulas (1-4) to (I-5) are 2
pyrazoloazole ring via a primary or tertiary carbon atom
Represents a group that is bonded to. In general formulas (I-1) to (I-5), X is a hydrogen atom,
rogen atom, carboxy group, or oxygen atom, nitrogen atom
Alternatively, it can be bonded to the carbon at the coupling position via a sulfur atom.
Represents a group that couples with a group that separates from coupling. R,, R4, R,, R6 or X becomes a divalent group,
This also includes cases where a space body is formed. Moreover, the general formula (I-1
) to (I-5) are in the vinyl monomer.
Sometimes R,, R4, R5 or R6 is a mere bond
or represents a linking group, through which general formula (I-1)
The moiety represented by ~(I-5) and the vinyl group are bonded. More specifically, R3, R4 and R5 are hydrogen atoms, halo
Gen atom (e.g. chlorine atom, bromine atom), alkyl group
(e.g. methyl, propyl, hexyl, trifluoro
Methyl, tridecyl, 3-(2,4-di-t-amyl
phenoxy)propyl, 2-dodecyloxyethyl, 3
-phenoxyprovir, 2-hexylsulfonyl-ethyl
cyclopentyl, benzyl), aryl groups (e.g.
, phenyl, 4-t-butylphenyl, 2.4-di-t
-amylphenyl, 4-tetradecanamidophenyl)
, heterocyclic groups (e.g., 2-furyl, 2-thienyl, 2
-pyrimidinyl, 2-benzothiazolyl), cyano group,
Alkoxy groups (e.g. methoxy, ethoxy, 2-methoxy)
xyethoxy, 2-dodecyloxyethoxy, 2-meth
sulfonylethoxy), aryloxy groups (e.g.
Phenoxy, 2-methylphenoxy, 4-tbutylphenylene
oxy), heterocyclic oxy groups (e.g. 2-benzimi
dazolyloxy), acyloxy groups (e.g. acetyloxy),
cy, hexadecanoyloxy), carbamoyloxy group
(e.g., N-phenylcarbamoyloxy, N-ethyl
carbamoyloxy), silyloxy groups (e.g.
methylsilyloxy), sulfonyloxy groups (e.g.
dodecylsulfonyloxy), acylamino groups (e.g.
, acetamide, benzamide, tetradecanamide,
α-(2,4-di-t-amylphenoxy)butylamide
γ-(3-t-butyl-4-hydroxyphenoxy)
) Butyramide, α-(4-(4-hydroxyphenyl)
sulfonyl) phenoxy) decanamide), anilino group
(e.g. phenylamino, 2-chloroanilino, 2-
Chloro-5-tetradecananilino, 2chloro-5-do
Decyloxycarbonylanilino, N-acetylanilino
No, 2-chloro-5-(α-(3-t-butyl-4-hyperoxygenate)
droxyphenoxy) dodecanamide) anilino), corrugated
Reid groups (e.g. phenylureido, methylureido
, NN-dibutylureido), imide groups (e.g., N-
Succinimide, 3-penzylhydantoinyl, 4-(
2-ethylhexanoylamino)phthalimide), sulfur
Famoylamino group (e.g. N,N-dipropylsulfur)
Famoylamino group, N-methyl-N-decylsulfa
moylamino), alkylthio groups (e.g. methylthio
, octylthio, tetradecylthio, 2-phenoxyene
Chilthio, 3-phenoxypropylthio, 3(4-t-
butylphenoxy)propylthio), arylthio group (
For example, phenylthio, 2-butoxy-5-t-octyl
ruphenylthio, 3-pentadecylphenylthio, 2-
Carboxyphenylthio, 4-tetradecanamidophe
nylthio), peterocyclic thio group (e.g. 2-penzothia
zolyldio), alkoxycarbonylamino groups (e.g.
, methoxycarbonylamino, tetradecyloxycal
bonylamino), aryloxycarbonylamino group (
For example, phenoxycarbonylamino, 2,4-di-t
ert-butylphenoxylponylamino), sulbo
amide groups (e.g. methanesulfonamide, hexade
Cansulfonamide, benzenesulfonamide, p-t
luenesulfonamide, octadecanesulfonamide,
2-Methyloxy-5-t-butylbenzenesulfona
carbamoyl group (e.g. N-ethyl carbamo), carbamoyl group (e.g. N-ethylcarbamo
yl, N, N-dibutylcarbamoyl, N-(2-dode
syloxyethyl)carbamoyl, N-methyl-N-do
Decylcarbamoyl, N-(3-(2,4-di-tert)
-amylphenoxy)propyl)carbamoyl), reed
group (e.g. acetyl, (24-di-tert-amino)
ruphenoxy) acetyl, benzoyl), sulfamoy
group (e.g., N-ethylsulfamoyl, NN-dipropylene)
lopylsulfamoyl, N-(2-dodecyloxyethyl
) Sulfamoyl, N-ethyl-N-dodecylsulfur
amoyl, NN-diethylsulfamoyl〉, sulfony
group (e.g. methanesulfonyl, octanesulfonyl)
, benzenesulfonyl, toluenesulfonyl), sulfur
linyl groups (e.g., octane sulfinyl, dodecyl
rufinyl, phenylsulfinyl), alkoxylic
Bonyl groups (e.g. methoxycarbonyl, butyloxy
carbonyl, dodecylcarbonyl, octadecylcarbo
), aryloxycarbonyl group (e.g. phenyl), aryloxycarbonyl group (e.g.
3-pentadecyloxycarbonyl, 3-pentadecyloxy-carbo
nil). at least 61 of R, , R4 or R5, and R6
is a pyrazoloazole via a secondary or tertiary carbon atom.
represents a group bonded to a ring. Let us explain these groups in detail.
If so, isopropyl group, t-butyl group, t-hexyl group
, cyclohexyl group, adamantyl group,
Sopropyl group, 1-phenoxy-1,1-dimethylmethy
group, α, α-dimethylbenzyl group, α, a-dimethyl
Phenylethyl group, α-ethylbenzyl group, 1-ethyl
-1-[4-(2-butoxy-5-teri knee)
octylbenzenesulfonamide) phenylcomethyl group
, 1-methyl-2-[4-(4-dodecyloxybenze)
sulfonamido)phenyl]ethyl group, l-methyl-
2-(2-year-old ctyloxy-5-tert-octylbe
(benzenesulfonamide) ethyl group, ■, l-dimethyl 2
-(2-octyloxy-5-tert-octylben
zenesulfonamido)ethyl group, 1-methyl-2-[2
-octyloxy-5-(2-octyloxy-5-t
ert-octylbenzenesulfonamide)benzene
sulfonamido]ethyl group, 1-ethyl-2-(2-dode
Siloxy 5-tert-octylbenzenesulfona
mido)ethyl group, 1-(2-hydroxyethyl)2-
((Z-[3-(2-octyloxy-5tert-o)
(cutylbenzenesulfonamide) phenoxy] dodeca
(amido)ethyl group, etc. To explain in detail about X, X is a hydrogen atom or a halogen atom.
(e.g. chlorine atom, bromine atom, iodine atom),
a boxyl group, or a group linked via an oxygen atom (for example, a
Setoxy, propanoyloxy, benzoyloxy, 2
．． 4-dichlorobenzoyloxy, ethoxyoxaroy
fluoroxy, bilvinyloxy, cinnamoyloxy,
phenoxy, 4-cyanophenoxy, 4-methanesulfone
Amidophenoxy, 4-methanesulfonylphenoxy,
α-Naphthoxy, 3-pentadecylphenoxy, benzene
carbonyloxy, ethoxy, 2-cyanoethyl
xy, benzyloxy, 2-phenethyloxy, 2-phenyloxy
phenoxyethoxy, 5-phenyltetrazolyloxy,
2-benzothiazolyloxy), a group linked via a nitrogen atom
(e.g., benzenesulfonamide, N-ethyltoluene)
sulfonamide, heptafluorobutanamide, 2,
3,4,5.6-pentafluorobenzamide, octa
sulfonamide, p-cyanophenylureido, NN
-diethylsulfamoylamino, 1-piperidyl, 5
．． 5-dimethyl 2,4-dioxo-3-oxazolidini
group, l-benzyl-ethoxy-3-hydantoynyl,
2N-1,l-dioxo-3(2H)-oxo-1,2
-Benzisothiazolyl, 2-oxo12-dihydro-
1-pyridinyl, imidazolyl, pyrazolyl, 3.5-
diethyl-1,2,4-triazol-1-yl, 5-
or 6-promobenzotriazol-1-yl, 5
-Methyl 1 2.3.4-triazol-1-yl, base
Nzuimidazolyl, 3-benzyl-1-hydantoinyl
, 1-benzyl-5-hexadecyloxy 3-hydant
inyl, 5-methyl-1-tetrazolyl, 4-methoxy
Phenylazo, 4-pivaloylaminophenylazo, 2
-hydroxy-4-0 propanoylphenylazo), a group linked via a sulfur atom
(e.g. phenylthio, 2-carboxyphenylthio
, 2-methoxy-5-t-octylphenylthio, 4-
Methanesulfonylphenylthio, 4-octanesulfone
amidophenylthio, 2-butoxyphenylthio, 2-
(2-hexanesulfonylethyl)-5-tert-o
cutylphenylthio, benzylthio, 2-cyanoethyl
thio, l-ethoxycarbonyltridecylthio, 5-ph
phenyl-2,3,4,5-tetrazolylthio,2-ben
Zothiazolylthio, 2-dodecylthio-5-thiopheny
ruthio, 2-phenyl-3-dodecyl-1,2,4-1
riazolyl-5-thio). Rs, R4, R5 or X becomes a divalent group to form a bis body
If we describe this divalent group in more detail,
, substituted or unsubstituted alkylene groups (e.g. methylene
, ethylene, 1-ethylethylene, 1.10-decylene
, -CH2C1(2-0-(:H2CI(□-L substitution or
or an unsubstituted phenylene group (for example, 1,4 phenylene
, 1.3-phenylene, -NHC:0-R? -CONH- group (R, is substituted or
Represents an unsubstituted alkylene group or phenylene group. )
The divalent group in which R6 becomes a divalent group to form a bis body is the above.
When the alkylene group is connected via a secondary or tertiary carbon atom
It is a group that binds to the pyrazoloazole ring. Those represented by general formulas (1-1) to (I-5) are vinyl
R3, R4 or R, when present in the monomer
The linking group used is an alkylene group (substituted or unsubstituted).
An alkylene group, such as methylene, ethylene, 1-methyl
ethylene, 110 decylene, -CHzCH20CH2
CH2-), phenylene group (substituted or unsubstituted phenylene group)
Nylene group, for example, 1,4-phenylene, 1,3-phenylene
henylene, -〇0C0 and aralkylene groups (including groups such as Lμ). The alkylene linking group represented by R6 is
, the above alkylene group has a secondary or tertiary carbon atom
Represents a group bonded to the pyrazoloazole ring via. The vinyl group in the vinyl monomer has the general formula (1-1
) to (I-5) having substituents other than those represented by
Including cases where Preferred substituents are a hydrogen atom, a chlorine atom,
or a lower alkyl group having 1 to 4 carbon atoms. Coupling with oxidation products of aromatic-grade amine developers
There is no non-chromogenic ethylene-like monomer such as acrylic acid, α
-chloroacrylic acid, α-alacrylic acid (e.g. meth
acrylic acid) and those derived from these acrylic acids.
ester or amide (e.g. acrylamide, n-butyl acryl)
amide, t-butylacrylamide, diacetone acrylic
ruamide, methacrylamide, methyl acrylate,
Ethyl acrylate, n-propyl acrylate, n-
Butyl acrylate, t-butyl acrylate, 1so
-Butyl acrylate, 2-ethylhexyl acrylate
g, n-octyl acrylate, lauryl acrylate,
Methyl methacrylate, ethyl methacrylate, n-butyl
Chil methacrylate and β-hydroxy methacrylate
g), methylene dibis acrylamide, vinyl ester
(e.g. vinyl acetate, vinyl propionate and
vinyl laurate), acrylonitrile, methacrylo
Nitriles, aromatic vinyl compounds (e.g. styrene and
its derivatives, vinyltoluene, divinylbenzene, vinyl
Ruacetophenone and sulfostyrene〉, itaconic acid
, citraconic acid, crotonic acid, vinylidene chloride,
vinyl alkyl ether (e.g. vinyl ethyl ether)
), maleic acid, male anhydride 4 Inic acid, maleic acid ester, N-vinyl-2-pyrroli
Don, N-vinylpyridine, and 2- and 4-vinylpyridine
Examples include lupyridine. Non-chromogenic ethylene used here
Including cases where two or more types of unsaturated monomers are used together.
. Examples of couplers included in the present invention are shown below, but are not limited to these.
It is not determined. (P-1) (P 2) (P 3) (P-4) (P-5) (P 6) 7 (P 7) (P 8) (P 9) (P 10) (P-11) ( P 12) (P 13) (P-14) (P 15) (P 16) (P 18) CH3 (P 19) (P 20) (P-21) (P 22) (P-23) (P 24 ) CH3 CH2NH5O2CH3 (P-25) (P 27) (P 28) (P 29) (P-30) (P 31) (P 32) (P 33) (P 34) (P 35) H3 of the present invention ( Represented by the general formulas I-1) to (I-5)
The couplers used are based on the methods described in the literature listed below.
It can be synthesized by The compound of general formula (I-1) is disclosed in JP-A-59162548.
The compound of general formula (■-2) is disclosed in JP-A-59-1
No. 71956, etc., the compound of general formula (I-3) is
Patent No. 3,725゜067 etc., the general formula (I-4)
The compound has the general formula (I
The compound of -5) is disclosed in U.S. Patent No. 3,061,432;
Synthesis methods are described in No. 3,369,597, etc.
ing. The chlorinated paraffin used in the present invention is directly chlorinated.
Chained, branched or cyclic paraffin or vinyl chloride
Chlorine-substituted unsaturated carbon such as chlorine, vinylidene chloride, allyl chloride, etc.
Polymers obtained from hydrogen chlorides or their monomers
It is a copolymer with other olefins and has a single composition.
It may be present or a mixture. chlorinated paraffin charcoal
The prime number is preferably 8 or more, and the molecular weight is preferably 250 or more.
It is below 10,000. Chlorine content in chlorinated paraffin
The amount is preferably 10% or more on average by weight, and
Preferably it is 30 to 80% on average. The following is used in the present invention.
Specific examples of chlorinated paraffins that can be used include their average composition and average composition.
Shown as average molecular weight and average chlorine content. Two or more types of chlorinated paraffins according to the present invention may be used in combination.
You can also do it. In addition, the amount of chlorinated paraffin used in the coupler of the present invention is
Usually 0.1g or more and 20g or less per 1g, preferably
0.3g to 1:5g, particularly preferably 1.0 to 5g
It is 3.7g. Too little chlorinated paraffin
The speed of color development and the density of color development become smaller.
Ru. Processing stability also deteriorates. On the other hand, if there is too much, it will be exposed to light.
The amount of oil in the material increases and the strength of the membrane decreases. Furthermore, the chlorinated paraffin of the present invention can be used for ordinary use as needed.
A mixture of high boiling point organic solvents may be used. this
In this case, as a high boiling point organic solvent used in combination, the following general formula
Those represented by (III) to (■) are preferred. General formula (III) W. 2 op=. I3 General formula (IV) 0D-W2 General formula (■) Vl, -0-L (wherein, WI, W2 and W3 are each substituted or
Unsubstituted alkyl group, cycloalkyl group, alkenyl group
5, represents an aryl group or a heterocyclic group, W4 is Wl
, OW, or SWl, where n is 1 to 5.
is an integer, and when n is 2 or more, W4 may be the same
They may be different, and in the general formula (■), WI and W
2 may form a fused ring. ) Among the compounds represented by general formulas (In) to (■), one
General formulas (III), (IV) and (V) are preferred. Further, the boiling point is preferably 160°C or higher. Specific examples of these high boiling point organic solvents are shown below. (0 1) P-GOC4H9)3 C2H5 0CH2CHC4Hg-++ / C2■15 2H5 (O16) C11H23CON(C2H5)2 The coupler of formula (I) according to the present invention may optionally contain a co-solvent.
(e.g. low-boiling organic solvents such as ethyl acetate) as well as salts.
in a high boiling point organic solvent containing at least one diluted paraffin.
Dissolve and emulsify and disperse this solution in an aqueous gelatin solution while stirring.
The resulting emulsified dispersion is mixed with a silver halide emulsion.
By this, the amount of water contained in the coating solution for the silver halide emulsion layer can be reduced.
It is preferable to The auxiliary organic solvent referred to here refers to an organic solvent useful during emulsion dispersion.
It can be carried out using a solvent, drying process during application, or the method described above.
It is something that is ultimately removed from the light-sensitive material.
Some degree of solubility in low boiling point organic solvents or water
Refers to a solvent that has the following properties and can be removed by washing with water, etc. In the present invention, various photographic materials are included in the silver halide emulsion layer.
A hydrophobic substance can be contained. Examples of photographic hydrophobic substances include colored couplers,
Color-forming coupler, developer, developer precursor, development inhibitor
agent precursor, ultraviolet absorber, development accelerator, hydro
Tone control agents such as quinones, dyes, dye release agents, antioxidants
agents, optical brighteners, antifading agents, and image stabilizers.
Ru. Among these, as an image stabilizer, a compound represented by general formula (II) is used.
It is preferable to contain at least one compound. In the present invention, the compound represented by formula (II) has a high boiling point.
The coupler described above may be drilled using a dotted organic solvent.
However, co-emulsification is preferred. The compound represented by the formula Mecho) will be explained in detail. In formula (IT), R3°, RII, R12, R13
The alkyl groups represented by and R8 are substituted and substituted, respectively.
and unsubstituted alkyl groups, as well as straight chain, branched and cyclic
Contains alkyl groups. As a substituent for the above substituted alkyl group
are the substituents mentioned earlier in the coupler explanation.
shall apply. The total number of carbon atoms from Rto to R14 is
is preferably 6 or more and 32 or less, and R8 has 3 carbon atoms.
-12 alkyl groups are preferred. More preferably, R
IQ and RII are methyl groups. The compound represented by formula (II) of the present invention is
l-100 mol %, preferably 1 to 100 mol%, based on coupler
It is added in an amount of 30 mol%. These compounds are magentacap
It is preferable to co-emulsify with Compound represented by the above formula (rr) used in the present invention
Specific examples are listed below, but are of course limited to these.
It's not something you can do. (IT-], ) (II-2) (II-3) (IT-4) C mountain ti3 shih3 shih3 (n-5) (IT-6) (H-7) (II-8) ( IT-10) (H-], 1) (n-t2) (n-13) CI(3-C-CH3 CH3 (Il 14) (II-15) (II-16) (II-17) (II -18) C1(a C-CHa CH3 The color photographic light-sensitive material of the present invention has a blue-sensitive halo on the support.
Silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitivity
A structure in which at least one silver halide emulsion layer is coated.
can be achieved. In general color photographic paper, the support
Normally it is painted on top in the above order, but this
It may be in a different order. In addition, infrared-sensitive halogen
a silver emulsion layer in place of at least one of the foregoing emulsion layers;
Can be used. These photosensitive emulsion layers contain
Silver halide emulsions sensitive to each wavelength range and photosensitive
A pigment that has a complementary color relationship with the light that
yellow, magenta against green and cyan against red.
The color can be reduced by containing a so-called color coupler that forms
It is possible to perform legal color reproduction. However, the photosensitive layer and cap
The color hue of color is a composition that does not have the above correspondence.
It's good as well. The silver halide emulsion used in the present invention is substantially iodine.
Silver chlorobromide or silver chloride that does not contain silver chloride
It can be preferably used. Here, silver iodide is essentially
Not containing means that the silver iodide content is 1 mol% or less, preferably
means 0.2 mol% or less. Halogen composition of emulsion
may be different or equal between particles, but between particles
Using emulsions with equal halogen composition, each grain has
It is easy to make the properties homogeneous. Also, halogenated
Regarding the halogen composition distribution inside silver emulsion grains,
The so-called uniform composition is the same in every part of the silver oxide grain.
The grains with a mold structure and the core inside the silver halide grains.
with a shell (layer or layers) surrounding it.
Particles with a so-called laminated structure with different halogen compositions, or
Different halogen compositions inside or on the surface of the particles in a non-layered manner
A structure with a part (the edge of the particle if it is on the particle surface)
, a structure in which parts of different compositions are joined on a corner or surface
) can be appropriately selected and used. high feeling
In order to obtain a higher degree of
It is advantageous to use
Yes. If the silver halide grains have the above structure,
In this case, the boundary between parts that differ in halogen composition is
Even if there is a clear boundary, mixed crystals may be formed due to compositional differences, resulting in failure.
Structures that may have clear boundaries or are actively continuous
It may be something with some variation. Regarding the halogen composition of these silver chlorobromide emulsions,
Silver bromide/silver chloride ratios can be used. this
The ratio can vary widely depending on the purpose, but the silver chloride ratio
is preferably 2% or more. In addition, photosensitive materials suitable for rapid processing contain high silver chloride content.
A so-called high silver chloride emulsion is preferably used. This is high salt
The silver chloride content of the silver emulsion is preferably 90 mol% or more,
More preferably 95 mol% or more. In such high silver chloride emulsions, the silver bromide localized layer is described first.
Inside the silver halide grains in a sticky layered or non-layered manner
and/or a structure having on the surface is preferable. Up
The halogen composition of the localized layer has a low silver bromide content.
It is preferably at least 10 mol%, and more than 20 mol%.
It is more preferable that And these localized layers
inside the particle, on the edge, corner, or surface of the particle surface.
However, in one preferred example, particles can be
Some of them are epitaxially grown.
can. On the other hand, it is possible to minimize the decrease in sensitivity when photosensitive materials are subjected to pressure.
High silver chloride milk with a silver chloride content of 90 mol% or more for the purpose of
In addition, the distribution of halogen composition within particles is small and even.
It is also preferred to use particles of monomorphic structure. In addition, in order to reduce the amount of replenishment of processing solution,
It is also effective to further increase the silver chloride content of the silver emulsion. In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferred.
used. Halogenation contained in the silver halide emulsion used in the present invention
Average particle size of silver particles (circle equivalent to the projected area of the particles)
Particle size is determined by the diameter and the number average is taken)
is preferably 0.1μ to 2μ. In addition, their particle size distribution has a coefficient of variation (particle size
standard deviation of the distribution divided by the average particle size) 20%
Hereinafter, a so-called monodisperse material of 15% or less is preferable.
Yes. At this time, in order to obtain a wide latitude, the above
Monodispersed emulsions may be blended in the same layer, or heavy
N coating is also preferably carried out. The shape of silver halide grains contained in photographic emulsions is cubic.
, regular (regu) such as a tetradecahedron or an octahedron.
lar) having a crystalline shape, such as spherical, plate-like, etc.
having an irregular crystal shape;
Alternatively, it is possible to use a combination of these forms.
Wear. Also, it is a mixture of crystals with various crystal forms.
It may consist of. In the present invention, among these
However, it is preferable that 50% or more of the particles have the above-mentioned regular crystal shape.
Preferably 70% or more, more preferably 90% or more
It is better to In addition to these, the average aspect ratio (yen equivalent diameter/
Tabular grains with a thickness of 5 or more, preferably 8 or more are projected
Emulsions whose area exceeds 50% of the total grains are also preferred.
It can be used in many ways. The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chimie et Ph1sique Pho by es
tographique (PaulMonte 1
Publishing, 1967), G., F., Duffin, P.
Hot. graphic Emulsion ChemisLr
y (published by Focal Press, 1966),
Maki V. L. Zelikman et al.
ng and Coating Photography
c Emuldion (published by Focal Press)
, 1964).
be able to. Namely, acidic method, neutral method 2, ammonia method
Any method such as A method may be used, and soluble silver salt and soluble halo
Methods for reacting gen salts include one-sided mixing method and simultaneous mixing method.
Any method as legal, and combinations thereof
May be used. The particles are exposed to an atmosphere rich in silver ions.
It is also possible to use a method in which the mixture is formed by
Ru. Production of silver halide as a form of simultaneous mixing method
A method of keeping the pHg in the liquid phase constant, that is, the so-called CO
You can also use the ndrold-doublegeno1 method.
. According to this method, the crystal shape is regular and the particle size is uniform.
A silver halide emulsion close to unity can be obtained. The silver halide emulsion used in the present invention is characterized by its emulsion grain formation.
or various polyvalent metal ions in the process of physical ripening.
Impurities can be introduced. Examples of compounds used include cadmium, zinc, lead,
Steel, salts such as thallium, or iron, which is a group II element,
Ruthenium, rhodium, palladium, osmium, iridium
Examples include salts or complex salts of dium, platinum, etc.
Ru. In particular, the above Group Ⅰ elements can be preferably used.
. The amount of these compounds added can vary widely depending on the purpose.
However, it is preferably 10-9 to 10-2 mol relative to silver halide.
Delicious. The silver halide emulsion used in the present invention is usually chemically sensitized.
and spectral sensitization. Regarding chemical sensitization methods, the addition of unstable sulfur compounds is a typical method.
sulfur sensitization, noble metal sensitization represented by gold sensitization,
Alternatively, reduction sensitization can be used alone or in combination.
can. Regarding compounds used for chemical sensitization,
Lower right corner of page 18 of the specification of Publication No. 62-215272 (closed)
-Those described on the upper right shelf of page 22 are preferably used. Spectral sensitization is applied to the emulsion of each layer in the light-sensitive material of the present invention.
This is done for the purpose of imparting spectral sensitivity to the desired wavelength range.
Ru. In the present invention, a wave that corresponds to the desired spectral sensitivity is
By adding a spectral sensitizing dye that absorbs light in a long range,
It is preferable to do so. Spectral sensitizing dye used at this time
For example, FoM, 11ete by Ilarmer
rocyclic compoundsCyanine
dies and related compounds
ds (John Wiley & 5ons (NeI
Published by York, London, 1964).
I can list what is listed. specific compound
Examples of the product and the spectral sensitization method are described in the above-mentioned Japanese Patent Application Laid-Open No. 62-21.
As stated in the upper right column of page 22 to page 38 of the specification of Publication No. 5272.
Those listed above are preferably used. The silver halide emulsion used in the present invention includes
Preventing fogging during processing, storage or photo processing,
Alternatively, various compounds may be used to stabilize photographic performance.
or their precursors can be added. these
A specific example of the compound is described in the above-mentioned JP-A No. 62-215272.
Those described on pages 39 to 72 of the publication specification are preferred.
Often used. In the emulsion used in the present invention, latent images are mainly formed on the grain surfaces.
The so-called surface latent image emulsion, or the latent image mainly consists of grains.
Which type of so-called internal latent image emulsion is formed inside the emulsion?
It may be from a pool. When the present invention is applied to color photosensitive materials, the color sensitivity
Optical materials include an oxidized product of an aromatic amine color developer and a cup.
The rings produce yellow, magenta, and cyan colors respectively.
yellow coupler, magenta coupler and cyanka
A puller is usually used. Cyan coupler and maple preferably used in the present invention
Zenta coupler (represented by the general formula (1) above)
The following general
Formulas (C-I), (C-11), (M-I) and (Y)
This is shown in . General formula (C-I) 11 General formula (C ■) H 2 General formula (MI) General formula (Y) In general formula (C-1) and ((, -II), R1
, R2 and R4 are substituted or unsubstituted aliphatic, aromatic
represents a group or a heterocyclic group, and R1, R3 and R6 are hydrogen
atom, halogen atom, aliphatic group, aromatic group or acyl
Represents an amino group, and R1 and R2 may represent a nitrogen-containing 5-membered ring.
Alternatively, it may represent a group of nonmetallic atoms forming a 6-membered ring. Y
l, Y2 is a hydrogen atom or a cup with an oxidized form of a developing agent
Represents a group that can leave during the ring reaction, n represents O or 1
figure. -C formula ((, -It), R5 is an aliphatic group
For example, methyl group, ethyl group,
Lopyl group, butyl group, pentadecyl group, Lert-methylene group
group, cyclohexyl group, cyclohexylmethyl group,
phenylthiomethyl group, dodecyloxyphenylthiomethyl group
group, butane-arsentomethyl group, methoxymethyl group, etc.
can be mentioned. Represented by the general formula (C-1) or ((, -II)
Preferred examples of cyan couplers are as follows. -S In formula (CI), preferable RI is an aryl group, a complex
It is a bare ring group, such as halogen atom, alkyl group, alkoxy
group, aryloxy group, acylamino group, acyl group, carbon
rubamoyl group, sulfonamide group, sulfamoyl group,
Sulfonyl group, sulfamide group, oxycarbonyl group,
More preferably, it is an aryl group substituted with a cyan group.
Delicious. In general formula (C-1), R3 and R2 do not form a ring
, R2 is preferably substituted or unsubstituted alkyl
group, aryl group, particularly preferably substituted aryl group.
It is an alkyl group substituted with xy, and R3 is preferably a hydrogen atom.
It is a child. In general formula (C-It), preferred R1 is substituted or
is an unsubstituted alkyl group or aryl group, and is particularly preferred.
or a substituted aryloxy-substituted alkyl group. In the general formula ((, -IT), R3 preferably has 2 carbon atoms.
~15 alkyl groups and a substituent having 1 or more carbon atoms
It is a methyl group, and substituents include an arylthio group and an arylthio group.
alkylthio group, acylamino group, aryloxy group, alkylthio group, acylamino group, aryloxy group,
A rukyloxy group is preferred. In general formula (C-11), R3 is an atom having 2 to 15 carbon atoms.
More preferably, it is an alkyl group, and has 2 to 4 carbon atoms.
Particularly preferred is an alkyl group. In the general formula (c-n), R6 is preferably a hydrogen atom,
chlorine atom and fluorine atom are particularly preferred.
Delicious. Preferred in general formulas (CI) and (CI[)
Preferred Y and Y2 are hydrogen atoms and halogens, respectively.
Atom, alkoxy group, aryloxy group, acyloxy
group, a sulfonamide group. In general formula (M-1), R7 and R7 are aryl
represents a group, and R6 is a hydrogen atom, an aliphatic or aromatic atom.
Represents a syl group, aliphatic or aromatic sulfonyl group,
Y3 represents a hydrogen atom or a leaving group. Aryl group for R7 and R7 (preferably phenyl group)
The permissible substituents for R are the permissible substituents for R,
Same as substituent, and when there are two or more substituents, the same
It may be the same or different. R8 is preferably a hydrogen atom
, aliphatic acyl group or sulfonyl group, particularly preferred
Preferably it is a hydrogen atom. Preferred Y is sulfur, oxygen or nitrogen atom
For example, U.S. Patent No. 4.3
51.897 and International Publication W08B104795
Particularly preferred are the sulfur atom-eliminating types as described.
. In general formula (Y), R11 is a halogen atom, an alkyl
represents an xy group, a trifluoromethyl group or an aryl group
, R1□ is a hydrogen atom, a halogen atom, or an alkoxy group
represents. A represents -NHCOR+ff. However, R
11 and R14 are each an alkyl group, an aryl group, or
Represents an acyl group. Y represents a leaving group. RI2 and R+i
, as a substituent for RI4, the permissible substituents for R+ are
The leaving group Y5 is preferably an oxygen atom.
Or it is of the type that leaves at either the nitrogen atom.
, nitrogen atom detachment type is particularly preferred. General formulas (C-I), (C-II), (M-I) and (
Specific examples of couplers represented by Y) are listed below. (C ■) zlls (C 3) C, +1. (C 4) 01] Cz I 5 (C-7) (C 8) Cz If s (C 9) (C 10) (C 12) H (C 13) (C 14) (C 15) (C 17) (C 18) (C-19) (C 20) (C 2]) (C 22) (M 1) C/ t (M 2) l (M-3) (M 7) (M 8) H3 CI( (Y-1) (Y 2) (Y 3) (Y-4) (Y 5) (Y 6) (Y 7) (Y-8) (Y-9) The above general formula (C-■) ~ The coupler represented by (Y) is
There is usually halogen in the silver halide emulsion layer constituting the photosensitive layer.
0.1 to 1.0 mol per mol of silver oxide, preferably 0
．． It is contained in an amount of 1 to 0.5 mol. In the present invention, for adding the coupler to the photosensitive layer
Various known techniques can be applied. usually
, by the oil droplet dispersion method known as the oil protection method.
After dissolving in the solvent, the surfactant
emulsify and disperse in an aqueous gelatin solution containing Or interface
Water or gelatin dissolved in coupler solution containing activator
A liquid may be added to form an oil-in-water dispersion with phase inversion. Also, alkali-soluble couplers are so-called Fisher
-Can also be dispersed by dispersion method. From the coupler dispersion,
By methods such as distillation, noodle washing or ultrafiltration.
, even when mixed with photographic emulsion after removing the low boiling point organic solvent.
good. As a dispersion medium for such couplers, dielectric constant (25”C
)2-20, high boiling point with refractive index (25°C) 1.5-1.7
Using organic solvents and/or water-insoluble polymer compounds
It is preferable to do so. As a high boiling point organic solvent, preferably one of the following forms % formula % (
) A high boiling point organic solvent is used. General formula (A) L 2 W General formula (B) W, -Co. 2 General formula (E) 2 (In the formula, W+, h2 and h3 are each substituted or
Substituted alkyl group, cycloalkyl group, alkenyl group,
Represents an aryl group or a heterocyclic group, W4 is a mountain, 0 mountain or
or S-W+, and n is an integer from ■ to 5.
, when n is 2 or more, h may be the same or different from each other.
Often, in -i formula (E), W and h2 form a fused ring.
). The high boiling point organic solvent that can be used in the present invention has the general formula (A).
Melting point is below 100°C and boiling point is 140°C other than
A compound that is immiscible with water above °C and is a good solvent for couplers.
If so, you can use it. The melting point of the high boiling point organic solvent is preferably
is below 80°C. The boiling point of the high boiling point organic solvent is preferably
or more than 160°C, more preferably 170°
C or higher. For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4. In addition, these couplers are compatible with the presence of the aforementioned high-boiling organic solvents.
under or in the absence of loadapul latex polymer (
For example, impregnated with U.S. Pat. No. 4,203,716)
, or soluble in water-insoluble and organic solvent-soluble polymers.
can be emulsified and dispersed in a hydrophilic colloid aqueous solution.
. Preferably, the specification of International Publication W 088100723
The homopolymer or copolymer described on pages 12 to 30 is
In particular, the use of acrylamide-based polymers improves color images.
This is preferable from the viewpoint of stabilization. The photosensitive material produced using the present invention contains a color antifoggant and
Hydroquinone derivatives, aminophenol derivatives
Contains gallic acid derivatives, ascorbic acid derivatives, etc.
You can. Various anti-fading agents may be used in the photosensitive material of the present invention.
I can do it. i.e. cyan, magenta and/or yellow
Organic anti-fading agents for images include hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
spirochromans, p-alkoxyphenols, bis
Hindered phenols, mainly phenols,
Edible acid derivatives, methylenedioxybenzenes, 75 nof
Enols, hindered amines and these compounds
Ace whose phenolic hydroxyl group is silylated or alkylated
Typical examples include ester or ester derivatives.
Ru. Also, (bissalicylaldoximide) nickel complex
and (bis-N, N-dialkyldithiocarbama)
D) Metal complexes such as nickel complexes can also be used.
Ru. Specific examples of organic anti-fade agents are described in the patent specifications below.
It is. Hydroquinones are U.S. Patent No. 2,360,290,
Same No. 2,418,613, Same No. 2,700,453
, No. 2.701.197, No. 2,728,659
No. 2□732.300, No. 2,735,76
No. 5, No. 3,982,944, No. 4,430, .
No. 125, British Patent No. 1.363,921, U.S. Patent
Tube No. 2.710,801, No. 2.816.028, etc.
6-hydroxychromans, 5-hydroxychromans
Orchids and spirochromans are covered by U.S. Patent No. 3,432,3
No. 00, No. 3.573.050, No. 3,574,
No. 627, No. 3.698゜909, No. 3,764
．． No. 337, JP-A-52-152225, etc.
The loin dunes are described in U.S. Patent No. 4,360.589, p.
-Alkoxyphenols are U.S. Patent No. 2,735,7
No. 65, British Patent No. 2.066.975, JP-A-59
-10539, Special Publication No. 57-19765, etc.
U.S. Patent No. 3,700,455
No. 52-72224, U.S. Pat. No. 4, 228
, No. 235, Special Publication No. 52-6623, etc.
Acid derivatives, methylenedioxybenzenes, aminopheno
U.S. Pat. No. 3,457,079 and U.S. Pat.
No. 4,332,886, Special Publication No. 56-21144, etc.
However, hindered amines are disclosed in U.S. Patent No. 3.336.1.
No. 35, No. 4, 268, . No. 593, British Patent No.
No. 1,326,889, No. 1,354,313, No.
No. 1.410,846, Special Publication No. 51-1420, Special Publication No.
Kaisho No. 58-114036, Kaisho No. 59-53846,
No. 59-78344, etc., metal complexes are described in the US patent
No. 4,050,938, No. 4,241゜155, English
National Patent No. 2,027,731 (A), etc.
Are listed. These compounds each correspond to
Usually 5 to 100 small flame caps for color couplers.
By co-emulsifying with the photosensitive layer and adding it to the photosensitive layer, it is possible to achieve the desired purpose.
can be achieved. Cyan dye image heat and especially light
In order to prevent deterioration due to
UV absorbers can be introduced into the layers on both sides adjacent to this layer.
more effective. As ultraviolet absorbers, aryl group-substituted hexyl
Triazole compounds (e.g. U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g.
For example, U.S. Pat. No. 3,314.794 and U.S. Pat. No. 3,352.
681), benzophenone compounds (e.g.
For example, those described in JP-A No. 46-2784), cinnamic acid
Ester compounds (e.g. U.S. Patent No. 3,705°805
No. 3,707,395), Pukuji
ene compounds (described in U.S. Pat. No. 4,045,229)
), or benzoxidol compounds (e.g.
National Patent No. 3,406,070 No. 3,677.672
or the one described in No. 4.271,307).
I can do that. UV-absorbing couplers (e.g. α-naf)
Tall-based cyan dye-forming couplers) and ultraviolet absorbing
Polymers such as these may also be used. These UV absorbers
may be mordanted in a particular layer. Among them, benzotriazo substituted with the above aryl group
A metal compound is preferred. In addition to the above-mentioned couplers, the following compounds may also be used:
It is preferable to use Especially pyrazoloazole capra
It is preferable to use it in combination with -. In other words, the aromatic amine developer remaining after color development processing
Chemically combined with drugs to be chemically inert and virtually colorless
Compound (F) that produces the compound and/or color developer
Oxidation of aromatic amine color developing agent remaining after image processing
Chemically bound to the body, chemically inert and virtually colorless
Using the compound (G) that produces the compound simultaneously or singly
For example, residual color development in the film during storage after processing may occur.
Color development due to the reaction between a developing agent or its oxidized product and a coupler
Prevents staining and other side effects caused by pigment production
preferred above. Preferred compounds as compound (F) are p-anisidine and
The second-order reaction rate constant of
(during Fate) is 1. Ofi/mol ・see −I
X10-' I! , reacts in the range of /mat-sec
It is a compound. The second-order reaction rate constant is based on JP-A-63-158545.
It can be measured by the method described in . If 2 is larger than this range, the compound itself is unstable.
may react with gelatin or water and decompose.
Ru. On the other hand, if R2 is smaller than this range, the remaining aroma
It reacts slowly with group amine developing agents and remains as a result.
Can prevent the side effects of aromatic alkali-based developing agents.
Sometimes there isn't. More preferable compounds (F) include the following general compounds.
It can be represented by the formula (Fl) or (Fll). General formula (F'1) R1-(A), -X General formula (Fil) R2-C=Y In the formula, R1 and R7 are each an aliphatic group, an aromatic group, or
represents a heterocyclic group. n represents 1 or O. A reacts with the aromatic agonist developer to form a chemical bond.
X represents a group that reacts with an aromatic amine developer and is released.
Represents a group that leaves. B is a hydrogen atom, an aliphatic group, an aromatic group
, represents a heterocyclic group, acyl group, or sulfonyl group,
Y is a compound in which the aromatic amine developing agent has the general formula (FII)
Represents a group that promotes addition to a substance. l here?
, and X, Y and R2 or B are bonded to each other to form a cyclic structure
It may be. Of the methods that chemically bond with residual aromatic amine developing agents
The typical examples are substitution reactions and addition reactions. Specifics of the compound represented by -i formula (F N, l'Fl[)
For examples, see JP-A-63-158545, JP-A-63-158545;
283338, European Patent Publication No. 298321, European Patent Publication No. 27
Those described in specifications such as No. 7589 are preferred.
stomach. On the other hand, the aromatic amine developer that remains after color development processing
Chemically bonded with the oxidized form of the drug, making it chemically inert and colorless
A more preferable compound (G) that produces a compound is
It can be represented by the following general formula (CI). General formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group.
vinegar. Z is a nucleophilic group or decomposes in the photosensitive material to become nucleophilic
represents a group that releases a group. Represented by general formula (Gl)
Compounds in which Z is Pearson's nucleophile 1lCI1. I
Value (R, G, Pearson, et al., J
, eight meters. Chem, Soc, 90.319 (1968>
) is preferably 5 or more, or a group derived therefrom.
Delicious. For specific examples of compounds represented by general formula (Gl),
European Patent Publication No. 255722, Japanese Patent Publication No. 1430/1986
No. 48, No. 62-229145, Patent Application No. 136-1983
No. 724, No. 62-214681, European Patent Publication 29
8321, 277589, etc.
is preferable. Further, details of the combination of the above compound (G) and compound (F)
Details are described in European Patent Publication No. 277589.
There is. The photosensitive material produced using the present invention contains hydrophilic colloids.
As a filter dye or as an irradiation layer
Water-soluble dyes are used to prevent halation and other purposes.
May contain dyes that become water-soluble through photographic processing.
stomach. Such dyes include oxonol dyes, hemioxonol dyes,
Sonol dye, styryl dye, merocyanine dye, shea
Included are nin dyes and azo dyes. Among them, Oxono
color dyes, hemioxonol dyes and merocyanine dyes
is useful. Binder that can be used in the emulsion layer of the light-sensitive material of the present invention
Alternatively, it is recommended to use gelatin as a protective colloid.
However, other hydrophilic colloids alone or with
Can be used with latin. In the present invention, gelatin may be lime-treated or acid-treated.
It doesn't matter if it was processed using . gelachi
For details on the manufacturing method of
Recular Chemistry of Gelatin (Academy)
Tsuku Press, published in 1964). The support used in the present invention is usually used for photographic materials.
Cellulose nitrate film and polyester film
Transparent films and reflective supports such as tyrene terephthalate
body can be used. For the purposes of this invention, a reflective support
It is more preferable to use ``reflective support j'' used in the present invention.
is the color formed in the silver halide emulsion layer by increasing its reflectivity.
This type of reflective support refers to something that makes the original image clearer.
titanium oxide, zinc oxide, and calcium carbonate on a support.
Hydrophobic material containing dispersed light-reflecting substances such as aluminum, calcium sulfate, etc.
Those coated with a transparent resin or those containing a dispersed light-reflecting substance.
Includes those using an aqueous resin as a support. for example
, baryta paper, polyethylene-coated paper, polypropylene-based
Contains a reflective layer or uses a reflective material
Transparent supports, e.g. glass plates, polyethylene telescopic
cellulose triacetate or cellulose nitrate.
Polyester film, polyamide film, polycarbonate
Bonate film, polystyrene film, vinyl chloride
There are resins, etc. As other reflective supports, specular reflective or type 2
Supports with diffusely reflective metal surfaces can be used.
Ru. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
It is better to roughen the metal surface or use metal powder.
It is better to use the body to make it diffusely reflective. As the metal
aluminum, tin, silver, magnesium or their alloys
The surface was obtained by rolling, plating, plating, etc.
It may be the surface of a metal plate, metal foil, or thin metal layer. Among these, it is preferable to obtain the metal by vapor-depositing the metal onto another substrate. Money
A layer of water-resistant resin, especially thermoplastic resin, is placed on the metal surface.
It is preferable to The side with a metal surface of the support of the invention
It is preferable to provide an antistatic layer on the opposite side. like this
For details of the support, see, for example, JP-A-61-210
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc. These supports can be appropriately selected depending on the purpose of use. As a light-reflecting substance, a white pigment in the presence of a surfactant is used.
It is best to thoroughly knead the pigment particles, and also coat the surface of the pigment particles with
It is preferable to use one treated with tetrahydric alcohol.
. Occupancy area ratio per specified unit area of white pigment fine particles
The ratio (%) most typically refers to the observed area,
Divide into unit areas of 6μ x 6μ and project onto that unit area.
Measure the occupied area ratio (%) of fine particles (Ri >
It can be determined and found. Change in occupied area ratio (%)
The coefficient is the standard deviation S of Ro with respect to the average value (R) of R4
It can be determined by the ratio s/R. target unit
The number (n) of position areas is preferably 6 or more. Therefore, the variable
The number s/R can be found by In the present invention, the occupied area ratio (%) of pigment fine particles is
The coefficient of variation is preferably 0.15 or less, particularly 0.12 or less.
. If it is 0.08 or less, the dispersibility of the particles is substantially "uniform".
It can be said that J. The color developing solution used in the development of the photosensitive material of the present invention is preferably
Preferably, the main ingredient is an aromatic primary amine color developing agent.
It is an alkaline aqueous solution. As this color developing agent
Aminophenol compounds are also useful;
Preferably, phenylenediamine compounds are used;
Table examples include 3-methyl-4-agono N, N-diedi
Luaniline, 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-a
Mino-N-ethyl-N-β-methanesulfonamidoethyl
Luaniline, 3-methyl-4-amino-N-ethyl-N
-〇-Methoxyethylaniline and their sulfates and salts
Examples include acid salts or P-1-luenesulfonate salts.
. Two or more of these compounds may be used in combination depending on the purpose.
can. The color developer is an alkali metal carbonate or phosphate.
Like ρ111! Buffers, bromide salts, iodide salts, benz
Imidazoles, benzothiazoles or mercaps
development inhibitors or antifoggants such as
It is common to include Also, if necessary, hydroxy
Ruamine, diethylhydroxylamine, sulfite, N
, N-hy, h such as lupoxymethylhydrazine
hydrazines, phenylsemicarbazides, trieta
Various types of preservatives such as nolamine and catechol sulfonic acids
agents, ethylene glycol, diethylene glycol, etc.
organic solvents, benzyl alcohol, polyethylene glyco
Rule 1. Development accelerators such as quaternary ammonium salts and amines
promoter, dye-forming coupler, competitive coupler 1-phenyl-
Auxiliary developing agents such as 3-pyrazolidone, viscosity-imparting agents,
Aminopolycarboxylic acid, aminopolyphosphonic acid, alkyl
phosphonic acid, phosphonocarboxylic acid, etc.
Various chelating agents, such as ethylenediaminetetraacetic acid,
trilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohetriacetic acid
Xanediaminetetraacetic acid, hydroxyethyliminodiacetic acid
, l-hydroxyethylidene-1,1-diphosphonic acid,
Nitrilo-N,N,N-trimethylenephosphonic acid, ethyl
Diamine-N,N,N'N'-tetramethylenephos
Phonic acid, ethylene glycol (0-hydroxyphenyl
(acetic acid) and their salts are representative examples.
Ru. In addition, when performing reversal processing, it is usually black and white development and reversal processing.
After processing, color development is performed. This black and white developer contains
Dihydroxybenzenes such as hydroquinone,
3-pyrazolidones such as Niru-3-pyrazolidone or
is an aminophenol such as N-methyl-P-aminophenol.
Known black and white developing agents such as polymers can be used alone or in combination.
Can be used together. The pI (pI) of these color developers and black and white developers is 9 to 12.
It is common that Also, replenishment of these developers
The amount depends on the color photographic material being processed, but generally
31 or less per square meter of photosensitive material, and the replenisher
By reducing the bromide ion concentration in
It can also be set to 0d or less. When reducing replenishment amount
By reducing the contact area with the air in the treatment tank
It is preferable to prevent evaporation of the liquid and air oxidation. Processing tank
The contact area between the photographic processing solution and the air is 0 as defined below.
It can be expressed as an aperture ratio of 0. In other words, aperture ratio = processing liquid
Contact area between air and air (cm”)/capacity of treatment liquid (cm’)
) The above aperture ratio is preferably 0.1 or less, more preferably
Preferably it is 0.001 to 0.05. As a method to reduce the aperture ratio in this way, the treatment tank
In addition to installing a shield such as a floating lid on the surface of the photographic processing solution,
Those who use the movable lid described in No. 62-241342
The slit described in JP-A No. 63-216050
Examples include development processing methods. Reducing the aperture ratio is effective for both color development and black and white development.
Not only the process, but also the subsequent processes, such as bleaching and bleach fixation.
Applicable to all processes such as application, fixation, washing, stabilization, etc.
It is preferable to do so. Additionally, measures are taken to suppress the accumulation of bromide ions in the developer.
By doing so, the amount of replenishment can also be reduced. The time for color development processing is usually set between 2 and 5 minutes.
However, high temperature, high pH, and high concentration of color developing agent are used.
It is also possible to further reduce processing time by using
Wear. After color development, the photographic emulsion layer is usually bleached. Bleaching treatment may be carried out simultaneously with fixing treatment.
(fixing process) may be performed separately. Even faster processing
In order to achieve
It can also be treated with two consecutive bleach-fix baths.
and fixing before bleach-fixing or bleach-fixing.
Depending on the purpose, bleaching can be carried out after the dyeing process.
Wear. As a bleaching agent, for example, a polyvalent agent such as iron (III)
A metal compound or the like is used. Iron is a typical bleaching agent.
Organic complex salts of (I[l), such as ethylenediaminetetraacetic acid
, diethylenetriaminepentaacetic acid, cyclohexanediamine
tetraacetic acid, methyliminodiacetic acid, 1. 3 diaminopro
Pantetraacetic acid, glycol ether diamine tetraacetic acid, etc.
aminopolycarboxylic acids or citric acid, tartaric acid,
Complex salts such as malic acid can be used. these
Of these, including ethylenediaminetetraacetic acid iron(III) complex salt,
Aminopolycarboxylic acid iron (I[[) complex salt is rapidly processed.
This is preferable from the viewpoints of safety and environmental pollution prevention. Furthermore, aminopo
Recarboxylic acid iron (m)ti salt can also be used in bleaching solutions.
It is also particularly useful in fixers. These aminopoly
Bleach solution or bleach constant using carboxylic acid iron (III) complex salt
The pH of the liquid that lands is usually 4.0 to 8.0, but it is difficult to process quickly.
It is also possible to process at an even lower pH for the purpose of oxidation. Bleach solution, bleach-fix solution, and their pre-baths may contain
bleach accelerators can be used. Specific examples of useful bleach accelerators are described in
Yes: U.S. Patent No. 3,893,858, West German Patent No. 1
．． No. 290,812, JP-A-53-95630, Lisa
Disclosure No. 17.129 (19
July 1978) Nomercap] group or disulfide
Compounds with fido bonds; JP-A-50-140129
U.S. Patent No. 3,706;
, 561; JP-A-58-16
Iodide salts described in No. 235; West German Patent No. 2.748,4
Poly03 oxyethylene compounds described in No. 30; described in Japanese Patent Publication No. 45-8836
Polyamine compounds listed above; bromide ions, etc. can be used.
. Among them, it has a mercapto group or a disulfide group.
Compounds are preferable from the viewpoint of having a large promoting effect, and are particularly suitable for the United States.
Patent No. 3.893.858, West German Patent No. 1,290,8
No. 12 and JP-A No. 53-95630 are preferred.
Delicious. Further described in U.S. Pat. No. 4,552,834
Also preferred are compounds. These bleach accelerators are used in light-sensitive materials.
May be added to. Bleaching and fixing color photosensitive materials for photography
These bleach accelerators are particularly effective when As a fixing agent, thiosulfate, thiocyanate, thioether
Examples include tel-based compounds, thioureas, large amounts of iodide salts, etc.
However, the use of thiosulfates is common and
Ammonium thiosulfate is the most widely used. bleaching
Preservatives for the fixer include sulfite, bisulfite, and P-
) Sulfinic acids such as luenesulfinic acid or carbon
Rubonyl bisulfite adducts are preferred. The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after 04 desilvering treatment.
It is. The amount of water used in the washing process is determined by the characteristics of the photosensitive material (e.g.
depending on the material used, such as couplers), the purpose, and even the washing water.
Refilling methods such as temperature, number of water washing tanks (number of stages), countercurrent flow, forward flow, etc.
, and can be set over a wide range depending on various other conditions. this
Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method.
Journal of Lbe 5ociety o
f Motion Picture and Te1e
Vision Engineers Vol. 64, p. 2
48-253 (May 1955 issue),
You can ask for it. According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be increased.
The residence time of water in the tank may be increased.
As a result, bacteria proliferate and the resulting suspended matter becomes photosensitive.
Problems such as adhesion to materials occur. Color photosensitivity of the present invention
As a solution to such problems in material processing,
Calcium ion described in JP-A No. 62-288838
, a highly effective method to reduce magnesium ions
Can be used. Also, in JP-A No. 57-8542
The isothiazolone compounds and thiabendazoles listed above,
Chlorinated disinfectants such as chlorinated sodium incyanurate,
Other benzotriazoles, etc., written by Hiroshi Horiguchi,
Manabu J (1986) Sankyo Publishing, Complete Sanitation Technology “Microorganisms”
Sterilization, sterilization, and anti-mold technology J (1982) Industrial technology
"Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society of Antibacterial and Antifungal Research (198
The fungicides described in 6) can also be used. The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. Washing water temperature, during washing
Although the time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.,
Generally, at 15-45°C for 20 seconds to 10 minutes, preferably
A range of 30 seconds to 5 minutes at 25-40°C is selected. Change
In addition, the photosensitive material of the present invention can be directly washed with a stabilizing solution instead of washing with water.
It can also be processed by In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
No. 3, No. 58-14834, No. 60-220345
All known methods described in can be used. Further, following the water washing treatment, a further stabilization treatment may be performed.
An example of this is the final bath for color photosensitive materials for photography.
A safe substance containing formalin and surfactant used as
One example is regular bathing. Various cow-rate agents and anti-mold agents can also be added to this stabilizing bath.
can. Overflow due to water washing and/or replenishment of stabilizing solution
The liquid can also be reused in other processes such as desilvering.
Ru. The silver halide color light-sensitive material of the present invention has simplification of processing.
Also, a color developing agent may be incorporated for the purpose of speeding up the process. Inside
For storage, various precursors of color developing agents are used.
It is preferable to be there. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15.159 and No. 15.159;
Aldol compounds described in No. 13,924, U.S. Pat.
, 719,492, JP-A-53-13
Examples include urethane compounds described in No. 5628.
Ru. The silver halide color photosensitive material of the present invention can be prepared as necessary.
, various 1-phenyl-3-
Pyrazolidones may also be incorporated. Typical compounds are
Described in 1982 No. 56-64339, No. 5707 144547, and No. 58-115438, etc.
It is listed. Various processing solutions in the present invention are kept at 10°C to 50°C.
used. Normally, the standard temperature is 33°C to 38°C.
However, higher temperatures can be used to accelerate the process and shorten the process time.
Reduce the temperature or conversely lower the temperature to improve image quality and stabilize the processing solution.
Qualitative improvements can be achieved. In addition, West German Patent No. 2,226,7 was developed to save silver on photosensitive materials.
No. 70 or U.S. Pat. No. 3,674,499.
Treatment using cobalt intensification or hydrogen peroxide intensification
You can. 08 (Example) The present invention will be specifically explained below with reference to Examples.
The invention is not limited thereto. Example 1 The following was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown in Figure 1 was prepared. The coating liquid is
It was prepared as follows. 19.1 g of yellow coupler (ExY) and color image
Stabilizer (Cpd-1) 4.4g and (Cpd-7)
To 1.8 g, add 27.2 cc of ethyl acetate and a medium (S
Add and dissolve 4.1g each of olv-3) and (Solv-6).
This solution was diluted with 10% sodium dodecylbenzenesulfonate.
185 cc of 10% gelatin aqueous solution containing 8 cc of aluminum
Emulsified and dispersed. On the other hand, silver chlorobromide emulsion (bromide i!80.
0 mol%, cubic; average particle size 0.854, variation coefficient
Number 0.08 and silver bromide 80.0%, cubic; average
With a particle size of 0.62ttm and a coefficient of variation of 0.07.
(mixed at a ratio of 1:3 (4 g molar ratio)) was sulfur-sensitized.
5 blue-sensitive sensitizing dyes shown below per mole of silver.
．． 0x10-' moles were prepared. The above emulsification
Mix and dissolve the dispersion and this emulsion to obtain the composition shown below.
A coating solution for the first layer was prepared. The coating liquid from the second layer to the seventh layer is the same as the -N coating liquid.
Prepared by method. The gelatin hardening agent for each layer is 1-oxygen.
C-3,5-dichloro-5-) riazine sodium salt
Using. The following spectral sensitizing dyes were used in each layer. Blue-sensitive emulsion layer SO, θ (5.0 x 10-' mol per 1 mol of halogenated tl
) green-sensitive emulsion layer (4.0XlO-' mole per mole of silver halide) and (halogen (7.0X10-5-Ele per mole of IJ) red-sensitive emulsion layer CzHs Io CsH++ (halogenated
0.9 x 10-' mol per mol of silver) in the red-sensitive emulsion layer.
For this, the following compound was added at 2 mol/mol of silver halide.
．． 6 x 10-' moles were added. 11 Also, for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer:
,■-(5-methylureidophenyl)-5-mercap
per mole of each halogenated totetrazole
4.0X10-6 mol, 3.0X10-5 mol, 1.0
x 10-' mole or 2-methyl-5(.1 mole of silver halide each of octylhydroquinone
8XIO-' moles, 2X10-" moles, 2x10
-2 mol was added. In addition, 4-hydroxy
C-6-methyl-1,3,3a,? -tetrazaindene
1.0 per mole of silver halide, respectively. ．． 2X10
-"mol, 1.1 x 10-"mol was added. In addition, for the red-sensitive emulsion layer, the following mercaptoimidazo
2 Xl0-' moles per mole of silver halide
and the following mercaptothiadiazoles with silver halide 1
4X10-' moles were added per mole. ■ The following dyes are added to the emulsion layer to prevent irradiation.
added. and (layer structure) The composition of each layer is shown below. Numbers are applied if (g/n
Represents (). The silver halide emulsion represents the coated amount in terms of silver. Support polyethylene laminated paper [white pigment (TiOz) and blue on the polyethylene on the first layer side
Contains taste dye (ulmarine blue)] No.-N (blue feeling N) The above-mentioned silver chlorobromide emulsion (AgBr: 80 mol%')
0.26 gelatin 1.83
Yellow coupler (Y to E) 0.
83 color image stabilizer (Cpd-1,)
0.19 color image stabilizer (Cpd-6)
0.08 solvent (Sol, v-2)
0.1B solvent (Sol, v-5)
0.18 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention layer
Stopping agent (Cpd-410,08 Solvent (Solv-1) 0.
16 solvent (Solv-3)
0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (AgBr 90 mol%, cubic, average grain
Child size 0.47μ, coefficient of variation 0.12, and Ag
Br 90 mol%, cubic, average particle size 0.36μ
, with a coefficient of variation of 0.09 at a ratio of 1:1 (static molar ratio
) 0.16 gelatin
1.79′? f7&#7'e-th
See Table 1 Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-7) Color image stabilizer (Cpd-8) 0.20 0.01 0.03 0. 04 Solvent See Table 1 Fourth layer (UV absorption N) Gelatin 1.58 UV
Absorber (UV-1) 0.47 color mixture
Inhibitor (Cpd-4) 0.05
Solvent (Solv-5) 0.
24 Fifth N (red sensitive layer) Silver chlorobromide emulsion (AgBr 70 mol%, cubic, average grain
Child size 0.49am, coefficient of variation 0.08, and A
gBr 70 mol%, cubic, average particle size 0.34
-1 coefficient of variation 0. IO and the ratio of l:2 (46 mo
0.23 gelatin
1.34 cyan coupler (E
xC) 0.30 color image stabilizer (Cp
d-5) Color image stabilizer (Cpd-6) Solvent (Solv-5) Sixth N (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-4) Solvent (Solv-4) Seventh layer (protective layer) Gelatin polyvinyl alcohol scum (modification degree 17%) Liquid paraffin 0.17 0.40 0.20 0.53 0.16 0.02 0.08 1.33 Lyle modified copolymer 0 .17 0.03 (Cpd-1) Color Image Stabilizer 15 (Cpd-2) Color Image Stabilizer (Cpd-3) Color Image Stabilizer 11 17 1G (Cpd-4) Color Mixing Preventer 11 (Cpd-5) 2:4:4 mixture (weight ratio) of color image stabilizer c4Hq(t) (Cpd-6) Color image stabilizer 14CH2-CH) -- CONflC4H1(t) Average molecular weight 80,000 18 (Cpd-8) Color image stabilizer I Cf 19 (UV-1) 4:2:4 mixture (weight ratio) of ultraviolet absorber 20 (Solv-1) Solvent (Solv-2) Solvent (Solv-3) Solvent 21 (Solv-4 )Solvent C00CIIHI? (CHz)s C00CIIHI? (Solv-5) Solvent CsH+tCHCH(CHt)tcOOcall+7\
1 22 (ExY) 1=1 mixture (molar ratio) with yellow coupler 23 (ExC) 1: mixture (molar ratio) of cyan coupler 24 First, each sample was tested with a sensitometer (manufactured by Fuji Photo Film Co., Ltd.,
FWH type, light source color temperature 3200°K),
Provided gradation exposure for 3-color separation filter for cytometry
. The exposure at this time was 250 CMS with an exposure time of 0.1 seconds.
I made sure to get the right amount of exposure. After the exposure, the sample undergoes the following processing steps (A
) was processed. Processing step (A) JLL Uri - One time and one stop color development 37'C 3 minutes 30 seconds bleach fixing
Wash at 33'C for 1 minute and 30 seconds. Dry at 24-34°C for 3 minutes.
70-80℃ 1 Composition of aromatic treatment liquid
is as follows. Shoj: Pisenzo Chu 2 Water 800
-diethylenetriaminepentaacetic acid t,o gni
Trilotriacetic acid 2.0g benzylua
Alcohol 15 all diethylene
Recall 10 d Sodium sulfite Potassium bromide Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl 4-agonoaniline sulfate Hydroxylamine sulfate 2.0 g 1.0 g 0 g 4.5 g Add 3.0g water and pH (25°C) Sadaharu Hoshiwata liquid water Ammonium thiosulfate (70%> Sodium sulfite Ethylenecya≧Ferontetraacetate (III) Add ammonium ethylenecyamine disodium tetraacetate water and pl+ (25'C) 1000 ml 10.25 00 50 1 8 5 5g 1000 ml 6.70 [Light resistance test] Each sample was tested for 35 days using an underglass outdoor irradiation table.
Measure the green light density before and after fading when exposed to sunlight.
Ta. Degree of color fading in high and low density areas due to light (fading rate)
was calculated as follows. High density part: Evaluation 2.0 at optical reflection density 2.0 before photobleaching Low density part: Evaluation 0.50-0.12 at optical reflection density 0.50 before photobleaching Note) D-Photobleaching Half-reflection density after light 0, 12 = density of the unexposed area before photobleaching [Processing stability test] As an evaluation of processing stability, the sample after exposure was bleached and fixed in the color developer of the processing step (A). 0.4d of liquid
Same treatment process (B) except that it was mixed at a ratio of /42
The treatment step was carried out in step (A) to give a concentration of 1.5.
The concentration change in the treatment step (B) at the point was determined. At? Magenta coupler for comparison (A-2) Comparison oil (V 2) (V-3) As is clear from Table 1, the conventional magenta coupler was
Dispersed with boiling point chlorinated paraffin or formula (I)
A pyrazoloazole coupler with a branched alkyl group of
Compared to the comparative sample used, the sample of the present invention is more robust to light.
properties have been significantly improved. In addition, the samples of the present invention were bleached.
Density when processed with a color developer containing a small amount of fixer
Changes are suppressed and process stability is excellent.
Recognize. 31 Example 2 The following was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown in Figure 1 was prepared. The coating liquid is
It was prepared as follows. No.-N coating solution preparation Yellow coupler (Ext) 19.1 g and color image
Stabilizer (Cpd-1) 4.4g and color image stabilizer (Cp
d-7) Add 27.2cc of ethyl acetate and the solution to 0.7g.
Add and dissolve 8.2g of solvent (Solv-1), and this solution
8cc of 10% sodium dodecylbenzenesulfonate
Emulsified and dispersed in 185cc of 10% gelatin aqueous solution containing
Ta. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.8
3-nia mixture of 8- and 0,70-(silver moiety)
(ratio). The coefficient of variation of particle size distribution is 0.08 and 0.08. l
Each O1 emulsion contains 0.2 mol% silver bromide locally on the grain surface.
The blue-sensitive sensitizing dye shown below was added per mole of ilW to
2.0X10-' for large size emulsions, respectively.
molar addition, and for small size emulsions, 2.
Sulfur sensitized after adding 5 x 10-' moles
was prepared. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following formula. The coating liquid for the second to seventh layers is the same as the coating liquid for the -layer.
Prepared by method. The gelatin hardening agent for each layer is 1-O
xy-3,5-dichloro-8-triazine sodium salt
was used. The following spectral sensitizing dyes were used in each layer. Blue-sensitive emulsion layer (per mole of silver halide, for large emulsions)
2.0 x 10-' moles each, also for small size emulsions
(2.5 x 101 mol each) green sensitive emulsion layer (halogenated t! per mol, for large size emulsion)
4.0 x 10-' mol for small size emulsions, 5
．． 6X10-' mol) and SO1θ 5O3H-N(CJs)z (per mol of silver halide, for large emulsions)
7.0 x 10-' mole, or 1 for small size emulsions
．． 0
0.9X]O-' moles, and for small size emulsions 1
．． 1×10−′ mol). For the red-sensitive emulsion layer, the following compounds are halogenated.
2.6 x 10-" mol was added per mol of silver. Also, 2.6 x 10-" mol was added per mol of silver.
, 1-(5-methylureidophenyl)-5-mercap
Totetrazole was added at 8.5X10-5 mol, 7.7X10-' and 2.5X]O-' mol per mole of monomer, respectively. Ta. The following dyes are added to the emulsion layer to prevent irradiation.
added. (Layered structure) Below are the precepts for each layer. The numbers represent the coating amount (g/'a)/.The silver halide emulsion represents the coating amount in terms of silver.Support polyethylene laminate paper [white 81t'l (Tid) on the polyethylene on the first layer side
y) and a bluish dye (ulmarine)] No.-N (blue-ish N) The above-mentioned silver chlorobromide emulsion 0.30 gelatin
1.86 yellow color
Puller (ExY) 0.82 color image standard
Fixed agent (Cpd-1) 0.19 solution
Solv-1,) 0.
35 color image stabilizer (Cpd-7)
0.06 Second N (color mixing prevention N) Gelatin 0.99 Color mixing prevention
Stopper (Cpd-5) 0.08 soluble
Solv-1 0.1
6 solvent (Solv-4) 0
．． 08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ)
and 0.39μ (Ag molar ratio
). The coefficient of variation of the particle size distribution is 0.10, O, OB,
Each emulsion contains 8 mol% of AgBrO locally on the grain surface.
0.12 gelatin
1.24 magenta coupler
See Table 2 Color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-3)
0.15 color image stabilizer (Cpd-4)
0.02 solvent
See Table 2 4th N (Ultraviolet absorption N) Gelatin 1.5 days UV rays
Absorber (UV-1) 0.47 color mixture
Inhibitor (Cpd-5) 0.05
Container (Solv-5)
0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion C cube, average grain size 0.58-
and 0.45ttm (Ag model).
(ratio). The coefficient of variation of particle size distribution is 0.09 and 0.1
1. In each emulsion, 6 mol% of AgBrO was locally contained in a part of the grain surface) 0.23 gelatin
Chin 1.34 cyan cap
Color (ExC) 0.32 color image stability
Agent (Cpd-6) 0.17 color image
Stabilizer (Cpd-7) 0.40
Color image stabilizer (Cpd-8) 0.
04? Container (Solv-6)
0.15 6th layer (ultraviolet absorption
layer) gelatin 0.53 ultraviolet rays
Absorbent (tlV-1) 0.16 mixture
Color inhibitor (Cpcl-5) 0.
02 Solvent (Solv-5)
(1.08 Seventh layer (protective layer) Gelatin 1.33 Polyvinyl
Acrylic modified copolymer of alcohol (modification degree 17%)
) 0.17 liquid paraffin
0.0340 41 (ExC) Cyan coupler R=C, 11, and C4I+. and H (2:4 = 4 by weight) (Cpd-1) Color image stabilizer 42 (Cpd-2) Color image stabilizer C00C21 (S (Cpd-3) Color image stabilizer (Cpd-4) Color Image stabilizer (Cpd-5) Color mixture prevention agent H 43 (Cpd-6) 2:4 = 4 mixture of color image stabilizers (weight ratio) (Cpd-7) Color image stabilizer → C1l□-CI+8-] (Cpd-8) Color Image Stabilizer H 44 (UV-1>Ultraviolet Absorber 45 (Solv-1) Solvent (Solv-2) 2:l mixture (volume ratio) of solvent (Solv-3) Solvent (Solv- 4) Solvent (So I Sea 5) Solvent C00CeH+7 (C11□).C00Call+q (Solv-6) Solvent First, each sample was exposed to light according to the method described in Example 1.
I got it. After exposure, the sample is processed using a paper processing machine.
, double the tank capacity for color development in the next processing step (A)
Perform continuous processing (running test) until replenishment.
Ta. Color development 35'C45 seconds 161111! 1
71 bleach window 30-35°C 45 seconds 215mfi
17 N rinse■ 30~35°C 20 seconds -to
jl! Rinse ■ 30~35°C 20 seconds -101ri
■ 30~35°C 20 seconds 35 (ld 10
ffi drying 70-80°C for 60 seconds
The composition of the liquid is as follows. Imperial 2-li blood release, 1lIL wave 凰Chung water
800m ri 800
ml Ethylenediamine-N, N N, N-tetramethylenephosphonic acid 1.5 g 2.0 g
47 Potassium bromide triethanolamine Sodium chloride Potassium carbonate N-ethyl-N-(β-methanesulfonate ethyl)-3-methyl-4 Aminoaniline sulfate N,N-bis(carboxymethyl)hydrazine Fluorescent brightener (WRITEX 4B. Manufactured by Sumitomo Chemical) Add 1.0 g water
1000m strain pH (25°C)
10.05M (tank liquid and replenisher liquid are the same) Ammonium hydrothiosulfate (70%) Sodium sulfite 5.0 5.5 0.015 g 8.0 g 12.0 g 1.4 g 25 g 25 g 7.0 7 .0 2.0g 1000ifi 10.45 400 mQ 100mJ! 7 Ethylenediamine ammonium 5 14 days Ethylene thiagon tetrastic acid disodium 5g Ambromide
Monium 40g Add water
1000mlpH (25'
C) 6.0-backs 2≦(
Tank fluid and refill fluid are the same) Ion exchange water (calcium,
51 From the results in Table 2, it can be concluded that the light fastness of the samples of the present invention is in the high concentration area.
It is extremely superior from low concentration to low concentration, and the balance fluctuation is small.
It is clear that the process stability is also excellent. (Effect of the invention) The silver halide color photographic light-sensitive material of the present invention has good color reproducibility.
It has excellent light fastness of dye images from high density areas to low density areas.
Provides significantly improved color photographs over the entire area. Sara
The silver halide color photographic material of the present invention is stable in processing.
For example, if bleach or bleach-fix solution is accidentally mixed in,
There is little change in the maximum color density even when processed with the color developer added.
Excellent structure and stability. Supplementary procedural device (voluntary) July 26, 1990

Claims (2)

[Claims] (1) In a silver halide color photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support, the boiling point of the silver halide emulsion layer at normal pressure is 175°C.
A silver halide color photographic material comprising at least one coupler represented by the following general formula (I) dispersed using at least one of the above chlorinated paraffins. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Za and Zb are respectively =CH-, ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ or = N-, R_
1 represents a hydrogen atom or a substituent, R_2 represents a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. The case where Za=Zb is a carbon-carbon double bond includes the case where it is part of an aromatic ring. R_1, R_2 or X may form a dimer or more multimer. However, if two R_2's exist in the same molecule, they may be the same or different. Also, I) If R_2 does not exist in the same molecule, R_1
or II) When R_2 exists in the same molecule, at least one of R_1 and R_2 represents a group bonded to the pyrazoloazole ring via a secondary or tertiary carbon atom. ) (2) The silver halide color photographic material according to claim (1), wherein the silver halide emulsion layer contains at least one compound represented by the following general formula (II). General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1_0, R_1_1, R_1_2 and R
_1_3 is an alkyl group having 1 to 18 carbon atoms, and R_1
_4 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 3. However, n is 2 to 3
, each R_1_4 may be the same or different, and when n is 1, R_1_4 is the alkyl group described above. )